Methyl Acrylate → (E)-methyl 3-(4-((6-methoxybenzo[b]thiophen-3-yl)oxy)phenyl)acrylate

HRID 632684노트

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HRID 632684 반응식
Br[C:2]1[CH:19]=[CH:18][C:5]([O:6][C:7]2[C:8]3[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][C:9]=3[S:10][CH:11]=2)=[CH:4][CH:3]=1.C(N(C(C)C)CC)(C)C.[C:29]([O:33][CH3:34])(=[O:32])[CH:30]=[CH2:31]>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:17][O:16][C:13]1[CH:14]=[CH:15][C:8]2[C:7]([O:6][C:5]3[CH:18]=[CH:19][C:2](/[CH:31]=[CH:30]/[C:29]([O:33][CH3:34])=[O:32])=[CH:3][CH:4]=3)=[CH:11][S:10][C:9]=2[CH:12]=1

참가 물질

6

반응물 3

HCID 7294Methyl Acrylate2회HCID 81531DiisopropylethylamineHCID 867306383-(4-Bromophenoxy)-6-methoxybenzo[b]thiophene

생성물 1

HCID 86730639(E)-methyl 3-(4-((6-methoxybenzo[b]thiophen-3-yl)oxy)phenyl)acrylate수율 64%

시약·촉매·용매 2

HCID 178418476HCID 178418476, 화합물촉매HCID 6228Dimethylformamide용매

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온도
120 °C

실험 절차

To a solution of 3-(4-bromophenoxy)-6-methoxybenzo[b]thiophene (125 g, 373 mmol) and Pd(PPh3)2Cl2 (13.09 g, 18.64 mmol) in DMF (2500 mL) and diisopropyl ethylamine (326 mL, 1864 mmol) at room temperature was added (subsurface) methyl acrylate (845 mL, 9322 mmol) over 3-4 hours. As the addition started, the reaction was heated at 120° C. for 13 hours. Methyl acrylate (150 mL, 1654.8 mmol) was added (subsurface). The reaction was heated at 120° C. for 1 hour. The mixture was cooled to RT. Excess methyl acrylate and diisopropyl ethylamine were remove in vacuo. The resulting mixture was filtered through celite pad and the cake was washed with EtOAc (2000 mL). The resulting mixture was washed with water (2×), dried with anhydrous Na2SO4 and concentrated in vacuo. The crude material was purified by column chromatography (SiO2, 5% to 500/(EtOAc/Heptane) to afford (E)-methyl 3-(4-((6-methoxybenzo[b]thiophen-3-yl)oxy)phenyl)acrylate (81 g, 238 mmol, 64% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm=1.46 (s, 3 H), 3.73 (s, 3 H), 6.28 (d, J=16.17 Hz, 1 H), 6.59 (s, 1 H), 6.90 (dd, J=8.59, 2.02 Hz, 1 H), 7.00 (d, J=8.59 Hz, 2 H), 7.21 (d, J=2.02 Hz, 1 H), 7.37-7.48 (m, 3 H), 7.59 (d, J=16.17 Hz, 1 H), LC/MS (m/z. MH+): 341.1.

후처리

  1. additionAs the addition
  2. temperatureThe reaction was heated at 120° C. for 1 hour
  3. temperatureThe mixture was cooled to RT
  4. customExcess methyl acrylate and diisopropyl ethylamine were remove in vacuo
  5. filtrationThe resulting mixture was filtered through celite pad
  6. washthe cake was washed with EtOAc (2000 mL)
  7. washThe resulting mixture was washed with water (2×)
  8. dry with materialdried with anhydrous Na2SO4
  9. concentrationconcentrated in vacuo
  10. customThe crude material was purified by column chromatography (SiO2, 5% to 500/(EtOAc/Heptane)

출처 및 근거

ORD 기록
ord-6ad2380fe40c411d85f6c3654641de69
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09321746B2

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